Polyurethane insulation foam composition comprising a stabilizing compound

ABSTRACT

A polyurethane insulation foam composition is disclosed herein. The polyurethane insulation foam comprises: (i) an aromatic isocyanate compound; (ii) an isocyanate reactive compound; (iii) water; (iv) a tertiary amine compound; (v) a hydrophilic carboxylic acid compound; (vi) a halogenated olefin compound; (vii) a stabilizing compound, and (vii) optionally, other additives.

BACKGROUND Field

The present disclosure relates generally to a polyurethane foamcomposition comprising halogenated olefins.

Background

Polyurethane insulation foams (e.g., rigid polyurethane insulationfoams) are widely used in the refrigeration and construction industriesas it offers good insulation performance at low densities. These foamshave conventionally been prepared by reacting an isocyanate compoundwith an isocyanate reactive compound in presence of a suitable blowingagent. With regard to blowing agents, chlorofluorocarbons (“CFCs”) andhydrochlorofluorocarbons (“HCFCs”), such as CFC-11 and HCFC-141b, havebeen widely used because they have been shown to produce closed-cellfoams having acceptable thermal insulation and dimensional stabilityproperties. However, in spite of these advantages, CFCs and HCFCs havefallen into disfavor as they may contribute to the depletion of ozone inthe earth's atmosphere and to the greenhouse effect. Accordingly, theuse of CFCs and HCFCs has been severely restricted.

More recently, saturated hydrofluorocarbons (“HFCs”) and hydrocarbons(“HCs”) have been used in polyurethane insulation foams since thesecompounds have a zero to near zero ozone depletion potential. Examplesof HFC's and HC's include HFC-365mfc, HFC-245fa, cyclopentane,n-pentane, and iso-pentane. Like CFCs and HCFCs, these compounds havetheir own shortcomings. The global warming potential of HFCs has beenconsidered relatively high and questions have been raised with regard totheir viability as a long term solution. While the global warmingpotential of HCs has been considered low, these compounds can be highlyflammable and some are deemed to be volatile organic compounds (“VOCs”).

Accordingly, there remains a need to develop a polyurethane insulationfoam composition using blowing agents having at least some of thefollowing characteristics: (i) zero to near zero ozone depletionproperties; (ii) zero to near zero global warming potential; (iii) notdeemed to be VOCs; and (iv) not overly cost prohibitive to deploy in asafe manner. Additionally, the foams made from such compositions shouldalso retain the superior insulation properties and low densities forwhich closed-cell rigid polyurethane foams are known.

DETAILED DESCRIPTION

As used herein, unless otherwise expressly specified, all numbers suchas those expressing values, ranges, amounts or percentages may be readas if prefaced by the word “about”, even if the term does not expresslyappear. Plural encompasses singular and vice versa.

As used herein, “plurality” means two or more while the term “number”means one or an integer greater than one.

As used herein, “includes” and like terms means “including withoutlimitation.”

When referring to any numerical range of values, such ranges areunderstood to include each and every number and/or fraction between thestated range minimum and maximum. For example, a range of “1 to 10” isintended to include all sub-ranges between (and including) the recitedminimum value of 1 and the recited maximum value of 10, that is, havinga minimum value equal to or greater than 1 and a maximum value of equalto or less than 10.

As used herein, “molecular weight” means weight average molecular weight(M_(w)) as determined by Gel Permeation Chromatography.

Unless otherwise stated herein, reference to any compounds shall alsoinclude any isomers (e.g., stereoisomers) of such compounds.

Polyurethane Insulation Foam Composition

It is well understood that foam formation from a polyurethane foamcomposition typically involves multiple reactions. The choice of thecompositions' components, such as catalyst and other ingredients, aredictated in part by the intended application (e.g., spray application,pour-in place application) or end use (e.g., insulation foam). Ingeneral, there may be three reactions that occur during the formation ofa foam product from a polyurethane foam composition. The first reactionis often referred to as the gelling reaction. The gelling reactioninvolves the formation of a urethane compound as an isocyanate compoundreacts with a polyol compound. The second reaction is referred to as theblowing reaction. The blowing reaction involves the formation of a ureacompound and the release of carbon dioxide as an isocyanate compoundreacts with water. The third reaction is referred to as the trimerreaction. The trimer reaction involves the formation of an isocyanuratecompound as an isocyanate compound reacts with another isocyanatecompound in the presence of a trimerization catalyst. Because the use ofthe trimerization catalyst is optional, the trimer reaction does notalways occur in the formation of a polyurethane foam product. Theaforementioned reactions take place at different rates and are dependenton a variety of variables such as temperature, catalyst level, catalysttype and other factors as well (e.g., the presence of either primary orsecondary hydroxyl groups in the polyols used). However, to producehigh-quality foam, the rates of the competing gelling, blowing, andtrimer reactions must be properly balanced to meet the need of a givenapplication/use while also ensuring that the internal cells of thepolyurethane foam product do not collapse prior to or during theformation of the polyurethane foam product (e.g., during a polyurethanecomposition's foam rise phase). Additionally, the rates of the competinggelling, blowing, and trimer reactions must be properly balanced toensure that the proper gel time, end of rise time, and cream time arebeing obtained from the polyurethane composition for a givenapplication.

For example, in a spray foam application the formulator must tailor thepolyurethane composition in a manner that would avoid any dripping ordraining from the polyurethane composition after the composition hasbeen sprayed onto a substrate (e.g., a wall or ceiling). This can beaccomplished by using water and a strong blowing catalyst in thepolyurethane composition to generate carbon dioxide (“CO₂”). Ideally, afine froth (which is caused by the generation of CO₂) would form withincouple of seconds of spraying the polyurethane composition onto thesubstrate thereby preventing any dripping or draining issues. Anotherfactor a formulator must consider in connection with spray foamapplications is a polyurethane composition's tack free time. Forexample, if a polyurethane composition has a short tack free time, thenit could lead to frequent clogging of an applicator's spray equipment.Alternatively, if a polyurethane composition has a long tack free time,then it could lead to deformation of the foam when an applicator's bodyinadvertently touches the foam after it has been applied onto asubstrate. Furthermore, if a polyurethane composition's gel time is tooslow, then the foam that begins to form on a substrate (e.g., a wall)might begin to sag as the components of the composition react.

For a pour-in-place application (e.g., foams used in a refrigerator,water heater, or wall panel) the presence of water and a strong blowingcatalyst in a polyurethane composition is required in order to resistvoid formation during the formation of the foam product. Voids candevelop within the internal cell structure of a foam product as it formsdue to air being introduced into the forming foam via liquid flow in themold before the onset of gelling. Another factor a formulator mustconsider in connection with pour-in-place applications is a polyurethanecomposition's gel time. If a polyurethane composition has a short geltime, then this can lead to the mold not being fully filled with thepolyurethane composition. Alternatively, if a polyurethane compositionhas a long gel time, then this can lead to long demold times for thefinal foam product.

While most tertiary amine catalysts used in a polyurethane compositionwill drive all three reactions described above to some extent, thecatalyst used in a polyurethane composition and the amount that it isused in such composition is often selected based on which reaction orreactions the formulator would like to favor/facilitate. For instance,if the formulator wishes to favor the gelling reaction, then theformulator would select catalysts that favor the gelling reaction (e.g.,N-ethylmorpholine) over other catalyst that do not favor such reaction(e.g., N,N,N′,N″,N″-pentamethyldiethylenetriamine). On the other hand,if the formulator wishes to favor the blowing reaction over the gellingreaction, then the formulator would select a catalyst that would favorthe blowing reaction (e.g., N,N,N′,N″,N″-pentamethyldiethylenetriamine).

In addition to tertiary amine catalysts, a polyurethane composition canalso comprise a halogenated olefin (“HFO”) blowing agent. The use ofsome HFOs, however, can result in the loss of reactivity of certainreactive components in a composition comprising a tertiary aminecatalyst due to an unintended adverse reaction between the HFO compoundand the tertiary amine catalyst. As will be explained in greater detailbelow, the aforementioned loss of reactivity can then lead to otherissues in the final foam due in part to the reaction products (e.g.,halogenated ions and amine salts) of the HFO compound and tertiary aminecatalyst used in the polyurethane composition

The potential of the HFO compound and tertiary amine reacting with oneanother is not only problematic in a one component polyurethane systembut it is equally problematic in cases where the polyurethane insulationfoam composition is provided as a two component system. A typical twocomponent polyurethane system is comprised of an “A-Side” and “B-Side.”The A-Side, which is also known as the iso-side, comprises an isocyanatecompound and, optionally, other compounds that do not react with theisocyanate compound. The B-Side, which is also known as the polyol-side,comprises an isocyanate reactive compound and, optionally, water,catalyst, blowing agents, foam-stabilizing surfactants, and otheradditive compounds. If the HFO and tertiary amine compounds are bothplaced in the B-Side, then there is a high probability that those twocompounds will begin reacting prior to the B-Side being mixed with theA-Side thereby creating the halogenated ion and amine salt reactionproducts mentioned above.

The halogenated ions and amine salt reaction products can have anegative impact on the polyurethane composition in several ways. Forinstance, the amine salts can precipitate out of the B-Side making theB-Side turbid. Additionally, the halogenated ions can decompose siliconebased surfactants that are widely used in various polyurethanecompositions. The depletion/degradation of the silicone based surfactanttypically leads to a foam product having lower insulative propertiesbecause the foam product will not only have a higher overall density butit will also have a larger and more open internal cell structure whichadversely affects the foam's insulative properties.

The polyurethane insulation foam composition of the present disclosuresolves the issues mentioned above by providing a polyurethane foamcomposition comprising blowing agents, which are not deemed to be VOCs,having zero to near zero ozone depletion properties and zero to nearzero global warming potential. Moreover, the polyurethane insulationfoam composition of the present disclosure also eliminates or reducesthe unintended reaction between HFO compounds and tertiary aminecatalysts present in the composition thereby extending not only theshelf-life of the composition but also allowing for the production of afoam product having consistent insulative properties and internal cellstructures.

The polyurethane insulation foam composition disclosed herein comprises:(i) an isocyanate compound; (ii) an isocyanate reactive compound; (iii)water; (iv) a tertiary amine compound; (v) a hydrophilic carboxylic acidcompound (vi) a halogenated olefin compound; (vii) a stabilizingcompound wherein the stabilizing compound comprises an un-alkoxylatedpolyhydroxy compound having 4 or more hydroxyl groups and (viii)optionally, other additives. In certain embodiments, the polyurethaneinsulation foam composition disclosed herein has a CT REACTIVE SHIFT(defined in the Examples below) less than or equal to 60 (e.g., lessthan or equal to 50 or 40 or 3025 or 20 or 15 or 10 or 5 or 1 or 0) anda TFT REACTIVE SHIFT (defined below in the Examples) less than or equalto 60 (e.g., less than or equal to 50 or 40 or 30 or 20 or 15 or 10 or 5or 1 or 0). In certain embodiments, the polyurethane insulation foamcomposition is a spray polyurethane insulation foam composition (e.g., aspray polyurethane insulation foam composition such as a closed cellspray polyurethane insulation foam composition). In other embodiments,the polyurethane insulation foam composition is a pour-in-placepolyurethane insulation foam composition such as a closed cellpour-in-play polyurethane foam insulation composition.

Component (i): Isocyanate Compound

The polyurethane insulation foam composition disclosed herein comprisesone or more isocyanate compounds. In some embodiments, the isocyanatecompound is a polyisocyanate compound. Suitable polyisocyanate compoundsthat may be used include aliphatic, araliphatic, and/or aromaticpolyisocyanates. The isocyanate compounds typically have the structureR—(NCO)_(x) where x is at least 2 and R comprises an aromatic,aliphatic, or combined aromatic/aliphatic group. Non-limiting examplesof suitable polyisocyanates include diphenylmethane diisocyanate (“MDI”)type isocyanates (e.g., 2,4′-, 2,2′-, 4,4′-MDI or mixtures thereof),mixtures of MDI and oligomers thereof (e.g., polymeric MDI or “crude”MDI), and the reaction products of polyisocyanates with componentscontaining isocyanate-reactive hydrogen atoms (e.g., polymericpolyisocyanates or prepolymers). Accordingly, suitable isocyanatecompounds that may be used include SUPRASEC® DNR isocyanate, SUPRASEC®2185 isocyanate, RUBINATE® M isocyanate, and RUBINATE® 1850 isocyanate,or combinations thereof. As used herein, SUPRASEC® and RUBINATE®isocyanates are all available from Huntsman International LLC.

Other examples of suitable isocyanate compounds also include tolylenediisocyanate (“TDI”) (e.g., 2,4 TDI, 2,6 TDI, or combinations thereof),hexamethylene diisocyanate (“HMDI” or “HDI”), isophorone diisocyanate(“IPDI”), butylene diisocyanate, trimethylhexamethylene diisocyanate,di(isocyanatocyclohexyl)methane (e.g.4,4′-diisocyanatodicyclohexylmethane), isocyanatomethyl-1,8-octanediisocyanate, tetramethylxylene diisocyanate (“TMXDI”),1,5-naphtalenediisocyanate (“NDI”), p-phenylenediisocyanate (“PPDI”),1,4-cyclohexanediisocyanate (“CDI”), tolidine diisocyanate (“TODI”), orcombinations thereof. Modified polyisocyanates containing isocyanurate,carbodiimide or uretonimine groups may also be employed as Component(i).

Blocked polyisocyanates can also be used as Component (i) provided thatthe reaction product has a deblocking temperature below the temperatureat which Component (i) will be reacted with Component (ii). Suitableblocked polyisocyanates can include the reaction product of: (a) aphenol or an oxime compound and a polyisocyanate, or (b) apolyisocyanate with an acid compound such as benzyl chloride,hydrochloric acid, thionyl chloride or combinations. In certainembodiments, the polyisocyanate may be blocked with the aforementionedcompounds prior to introduction into the reactive ingredients/componentsused to in the composition disclosed herein.

Mixtures of isocyanates, for example, a mixture of TDI isomers (e.g.,mixtures of 2,4- and 2,6-TDI isomers) or mixtures of di- and higherpolyisocyanates produced by phosgenation of aniline/formaldehydecondensates may also be used as Component (i).

In some embodiments, the isocyanate compound is liquid at roomtemperature. A mixture of isocyanate compounds may be produced inaccordance with any technique known in the art. The isomer content ofthe diphenyl-methane diisocyanate may be brought within the requiredranges, if necessary, by techniques that are well known in the art. Forexample, one technique for changing isomer content is to add monomericMDI (e.g., 2,4-MDI) to a mixture of MDI containing an amount ofpolymeric MDI (e.g., MDI comprising 30% to 80% w/w 4,4′-MDI and theremainder of the MDI comprising MDI oligomers and MDI homologues) thatis higher than desired.

Component (i) can comprise 30% to 65% (e.g., 33% to 62% or 35% to 60%)by weight of the polyurethane insulation foam composition based thetotal weight of the composition.

Component (ii): Isocyanate Reactive Compound

Any of the known organic compounds containing at least two isocyanatereactive moieties per molecule may be employed as the isocyanatereactive compound. For example, polyol compounds or mixtures thereofthat are liquid at 25° C., have a molecular weight ranging from 60 to10,000 (e.g., 300 to 10,000 or less than 5,000), a nominal hydroxylfunctionality of at least 2, and a hydroxyl equivalent weight of 30 to2000 (e.g., 30 to 1,500 or 30 to 800) can be used as Component (ii).

Examples of suitable polyols that may be used as Component (ii) includepolyether polyols, such as those made by addition of alkylene oxides toinitiators, containing from 2 to 8 active hydrogen atoms per molecule.In some embodiments, the aforementioned initiators include glycols,glycerol, trimethylolpropane, triethanolamine, pentaerythritol,sorbitol, sucrose, ethylenediamine, ethanolamine, diethanolamine,aniline, toluenediamines (e.g., 2,4 and 2,6 toluenediamines),polymethylene polyphenylene polyamines, N-alkylphenylene-diamines,o-chloro-aniline, p-aminoaniline, diaminonaphthalene, or combinationsthereof. Suitable alkylene oxides that may be used to form the polyetherpolyols include ethylene oxide, propylene oxide, and butylene oxide, orcombinations thereof.

Other suitable polyol compounds that may be used as Component (ii)include Mannich polyols having a nominal hydroxyl functionality of atleast 2, and having at least one secondary or tertiary amine nitrogenatom per molecule. In some embodiments, Mannich polyols are thecondensates of an aromatic compound, an aldehyde, and an alkanol amine.For example, a Mannich condensate may be produced by the condensation ofeither or both of phenol and an alkylphenol with formaldehyde and one ormore of monoethanolamine, diethanolamine, and diisopronolamine. In someembodiments, the Mannich condensates comprise the reaction products ofphenol or nonylphenol with formaldehyde and diethanolamine. The Mannichcondensates of the present invention may be made by any known process.In some embodiments, the Mannich condensates serve as initiators foralkoxylation. Any alkylene oxide (e.g., those alkylene oxides mentionedabove) may be used for alkoxylating one or more Mannich condensates.When polymerization is completed, the Mannich polyol comprises primaryhydroxyl groups and/or secondary hydroxyl groups bound to aliphaticcarbon atoms.

In certain embodiments, the polyols that are used are polyether polyolsthat comprise propylene oxide (“PO”), ethylene oxide (“EO”), or acombination of PO and EO groups or moieties in the polymeric structureof the polyols. These PO and EO units may be arranged randomly or inblock sections throughout the polymeric structure. In certainembodiments, the EO content of the polyol ranges from 0 to 100% byweight based on the total weight of the polyol (e.g., 50% to 100% byweight). In some embodiments, the PO content of the polyol ranges from100 to 0% by weight based on the total weight of the polyol (e.g., 100%to 50% by weight). Accordingly, in some embodiments, the EO content of apolyol can range from 99% to 33% by weight of the polyol while the POcontent ranges from 1% to 67% by weight of the polyol. Moreover, in someembodiments, the EO and/or PO units can either be located terminally onthe polymeric structure of the polyol or within the interior sections ofthe polymeric backbone structure of the polyol. Suitable polyetherpolyols include poly(oxyethylene oxypropylene) diols and triols obtainedby the sequential addition of propylene and ethylene oxides to di- ortrifunctional initiators that are known in the art. In certainembodiments, Component (ii) comprises the aforementioned diols or triolsor, alternatively, Component (ii) can comprise a mixture of these diolsand triols.

The aforementioned polyether polyols also include the reaction productsobtained by the polymerization of ethylene oxide with another cyclicoxide (e.g., propylene oxide) in the presence of polyfunctionalinitiators such as water and low molecular weight polyols. Suitable lowmolecular weight polyols include ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, cyclohexane dimethanol,resorcinol, bisphenol A, glycerol, trimethylolopropane,1,2,6-hexantriol, pentaerythritol, or combinations thereof.

Polyester polyols that can be used as Component (ii) include polyestershaving a linear polymeric structure and a number average molecularweight (Mn) ranging from about 500 to about 10,000 (e.g., preferablyfrom about 700 to about 5,000 or 700 to about 4,000) and an acid numbergenerally less than 1.3 (e.g., less than 0.8). The molecular weight isdetermined by assay of the terminal functional groups and is related tothe number average molecular weight. The polyester polymers can beproduced using techniques known in the art such as: (1) anesterification reaction of one or more glycols with one or moredicarboxylic acids or anhydrides; or (2) a transesterification reaction(i.e. the reaction of one or more glycols with esters of dicarboxylicacids). Mole ratios generally in excess of more than one mole of glycolto acid are preferred so as to obtain linear polymeric chains havingterminal hydroxyl groups. Suitable polyester polyols also includevarious lactones that are typically made from caprolactone and abifunctional initiator such as diethylene glycol. The dicarboxylic acidsof the desired polyester can be aliphatic, cycloaliphatic, aromatic, orcombinations thereof. Suitable dicarboxylic acids which can be usedalone or in mixtures generally have a total of from 4 to 15 carbon atomsinclude succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic,dodecanedioic, isophthalic, terephthalic, cyclohexane dicarboxylic, orcombinations thereof. Anhydrides of the aforementioned dicarboxylicacids (e.g., phthalic anhydride, tetrahydrophthalic anhydride, orcombinations thereof) can also be used. In some embodiments, adipic acidis the preferred acid. The glycols used to form suitable polyesterpolyols can include aliphatic and aromatic glycols having a total offrom 2 to 12 carbon atoms. Examples of such glycols include ethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethyleneglycol, dodecamethylene glycol, or combinations thereof.

Additional examples of suitable polyols include hydroxyl-terminatedpolythioethers, polyamides, polyesteramides, polycarbonates,polyacetals, polyolefins, polysiloxanes, and simple glycols such asethylene glycol, butanediols, diethylene glycol, triethylene glycol, thepropylene glycols, dipropylene glycol, tripropylene glycol, and mixturesthereof.

Additional examples of suitable polyols include those derived from anatural source, such as plant oil, fish oil, lard, and tallow oil. Plantbased polyols may be made from any plant oil or oil blends containingsites of unsaturation, including, but not limited to, soybean oil,castor oil, palm oil, canola oil, linseed oil, rapeseed oil, sunfloweroil, safflower oil, olive oil, peanut oil, sesame seed oil, cotton seedoil, walnut oil, and tung oil.

The active hydrogen-containing material may contain other isocyanatereactive material such as, without limitation, polyamines andpolythiols. Suitable polyamines include primary and secondaryamine-terminated polyethers, aromatic diamines such as diethyltoluenediamine and the like, aromatic polyamines, and combinations thereof.

Component (ii) can comprise 20% to 50% (e.g., 23% to 47% or 25% to 45%)by weight of the polyurethane insulation foam composition based thetotal weight of the composition.

Component (iii): Water

The polyurethane insulation foam composition disclosed herein compriseswater. While water can be considered an isocyanate reactive compound,for purposes of this disclosure water shall be considered a distinctcomponent from Component (ii). In other words, the polyurethaneinsulation foam composition disclosed herein comprises not onlyComponent (ii) but water as well.

Any type of purified water can be used as Component (iii) provided thatit has been filtered or processed to remove impurities. Suitable typesof water include distilled water and water that has been purified viaone or more of the following processes: capacitive deionization, reverseosmosis, carbon filtering, microfiltration, ultrafiltration, ultravioletoxidation, and/or electrodeionization.

Component (iii) can comprise 0.25% to 2.5% (e.g., 0.4% to 9% or 3% to8%) by weight of the polyurethane insulation foam composition based onthe total weight of the composition.

Component (iv): Tertiary Amine Compound & Other Optional Catalysts

The polyurethane insulation foam composition disclosed herein comprisesa one or more tertiary amine compounds. In some embodiments, thetertiary amine compound has the structure of Formula (I).

R₁R₂N—CH₂—CH₂—X—CH₂—CH₂—Y  Formula (I):

-   -   wherein        -   R₁ and R₂ are independently C₁-C₄ alkyl or C₂-C₄ alkanol;        -   X is Oxygen or N—R₃ wherein R₃ is C₁-C₄ alkyl or C₂-C₄            alkanol or OH; and        -   Y is OH or NR₄R₅ wherein R₄ and R₅ are independently C₁-C₄            alkyl or C₂-C₄ alkanol.

Suitable amine catalyst compounds comprising at least one tertiary groupinclude bis-(2-dimethylaminoethyl)ether (e.g., JEFFCAT® ZF-20 catalyst,DABCO BL-19 available from Evonik Industries AG, and Niax A-99),N,N,N′-trimethyl-N′-hydroxyethylbisaminoethylether (e.g., JEFFCAT® ZF-10catalyst), N-(3-dimethylaminopropyl)-N,N-diisopropanolamine (e.g.,JEFFCAT® DPA catalyst), N,N-dimethylethanolamine (e.g., JEFFCAT® DMEAcatalyst), blends of N,N-dimethylethanolamine aniethylene diamine (e.g.,JEFFCAT® TD-20 catalyst), N,N-dimethylcyclohexylamine (e.g., JEFFCAT®DMCHA catalyst; N-methyldicyclohexylamine (e.g., POLYCAT 12 availablefrom Evonik Industries AG), benzyldimethylamine (e.g., JEFFCAT® BDMAcatalyst), pentamethyldiethylenetriamine (e.g., JEFFCAT® PMDETAcatalyst), N,N,N′,N″,N″-pentamethyldipropylenetriamine (e.g., JEFFCAT®ZR-40 catalyst), N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine (e.g,JEFFCAT® ZR-50 catalyst),N′-(3-(dimethylamino)propyl-N,N-dimethyl-1,3-propanediamine (e.g.,JEFFCAT® Z-130 catalyst), 2-(2-dimethylaminoethoxy)ethanol (e.g.,JEFFCAT® ZR-70 catalyst), N,N,N′-trimethylaminoethyl-ethanolamine (e.g.,JEFFCAT® Z-110 catalyst, DABCO T available from Evonik Industries AG,and TOYOCAT-RX5 available from Tosho Corporation),2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol (e.g., DABCO NE200catalyst available from Evonik),N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether (e.g., DABCONE300 catalyst available from Evonik),N,N,N′,N′,N″-pentamethyl-diethylenetriamine (e.g., Kaolizer #3),N,N,N′,N′-tetramethylenediamine (e.g., TOYOCAT-TE available from ToshoCorporation), N-ethylmorpholine (e.g, JEFFCAT® NEM catalyst),N-methylmorpholine (e.g., JEFFCAT® NMM catalyst),4-methoxyethylmorpholine, N,N′dimethylpiperzine (e.g, JEFFCAT® DMPcatalyst), 2,2′dimorpholinodiethylether (e.g., JEFFCAT® DMDEE catalyst),1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine (e.g., JEFFCAT®TR-90 catalyst), 1-Propanamine, 3-(2-(dimethylamino)ethoxy), substitutedimidazoles (e.g., 1-methylimidazole, 1,2-dimethlyimidazol (e.g., DABCO2040 available from Evonik Industries AG and TOYOCAT DM70 available fromTosho Corporation), 1-methyl-2-hydroxyethylimidazole (e.g.,N-(3-aminopropyl)imidazole, 1-n-butyl-2-methylimidazole,1-iso-butyl-2-methylimidazole, N,N′-dimethylpiperazines),bis-substituted piperazines (e.g., aminoethylpiperazine,N,N′,N′-trimethyl aminoethylpiperazine or bis-(N-methylpiperazine)urea), N-methylpyrrolidines and substitutedmethylpyrrolidines (e.g., 2-aminoethyl-N-methylpyrrolidine orbis-(N-methylpyrrolidine)ethyl urea), 3-dimethylaminopropylamine,N,N,N″,N″-tetramethyldipropylenetriamine, tetramethylguanidine,1,2-bis-diisopropanol, or combinations thereof. Other examples of aminecatalysts include N-alkylmorpholines, N-butylmorpholine anddimorpholinodiethylether, N,N′-dimethylaminoethanol, N,N-dimethylaminoethoxyethanol, bis-(dimethylaminopropyl)-amino-2-propanol,bis-(dimethylamino)-2-propanol, bis-(N,N-dimethylamino)ethylether;N,N,N′-trimethyl-N′hydroxyethyl-bis-(aminoethyl)ether; N,N-dimethylamino ethyl-N′-methyl amino ethanol; tetramethyliminobispropylamine;N,N-dimethyl-p-toluidine; diethyltoluenediamine (Ethacure 100);3,5-dimethylthio-2,4-toluenediamine (Ethacure 300);poly(oxypropylene)triamine (JEFFAMINE® T-5000) reactive acid blockedcatalysts (e.g., phenolic acid salt of 1,8-diazabicyclo(5,4,0)undecene-7(POLYCAT SA-1), JEFFCAT® LED and JEFFCAT® ZF brand catalysts), orcombinations thereof.

Other amine catalysts which may be used polyurethane compositiondisclosed herein may be found in Appendix D in “Dow PolyurethanesFlexible Foams” by Herrington et al. at pages D.1-D.23 (1997), which isincorporated herein by reference. Further examples may be found in“JEFFCAT® Amine Catalysts for the Polyurethane Industry” versionJCT-0910 which is incorporated herein by reference.

Non-amine catalyst compounds may be used in combination with thetertiary amine compounds that comprise Component (iv). Suitablenon-amine catalyst compound that can be used include organo-metalliccompounds (e.g., organic salts of transition metals such as titanium,iron, nickel), post-transition metals (e.g., zinc, tin and bismuth),alkali metals (e.g., lithium, sodium and potassium), alkaline earthmetals (e.g., magnesium and calcium), or combinations thereof. Othersuitable non-amine catalyst compounds include ferric chloride, ferricacetylacetonate, zinc salts of carboxylic acids, zinc 2-ethylhexanoate,stannous chloride, stannic chloride, tin salts of carboxylic acids,dialkyl tin salts of carboxylic acids, tin (II) 2-ethylhexanoate,dibutyltin dilaurate (e.g., DABCO T-12 available from Evonik IndustriesAG), dimethyltin dimercaptide (e.g., FOMREZ UL-22 available fromMomentive Performance Materials Inc.), bismuth (Ill) carboxylate salts(e.g., bismuth(2-ethylhexanote)), bismuth neodecanoate (DABCO MB-20available from Evonik Industries AG), bismuth pivalate, bismuth-basedcatalysts (e.g., the compounds identified in US Patent Pub. No.016/020888), 1,1′,1″,1′″-(1,2-ethanediyldinitrilo)tetrakis[2-propanol]neodecanoate complexes (e.g., BICAT 8840 available from ShepherdChemicals Co.), 2,2′,2″,2′″-(1,2-ethanediyldinitrilo)tetrakis[ethanol]neodecanoate complexes (e.g., BICAT 8842 available from ShepherdChemicals Co.), K-KAT XC-C227 bismuth salt (available from KingIndustries), sodium acetate, sodiumN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate (JEFFCAT® TR52),bismuth(2-ethylhexanote), or combinations thereof.

Suitable trimerization catalysts that may be used in combination withthe catalysts listed above (i.e., Component (iv) and/or the non-aminecatalyst compounds) include potassium salts of carboxylic acids (e.g.,potassium acetate, potassium pivlate, potassium octoate, potassiumtriethylacetate, potassium neoheptanoate, potassium neooctanoate),quaternary ammonium carboxylates (e.g.,(2-hydroxypropyl)trimethylammonium 2-ethylhexanoate (“TMR”),(2-hydroxypropyl)trimethylammonium formate (“TMR-2”),tetramethylammonium pivalate, tetramethylammonium triethylacetate,TOYOCAT TRX (available from Tosoh, Corp)), or combinations thereof.

Component (iv) can comprise 0.5% to 4% (e.g., 0.7% to 3.7% or 0.5% to3.5%) by weight of the polyurethane insulation foam composition based onthe total weight of the composition. If used in combination with otheramine or non-amine catalysts, then such catalysts (i.e., not thecompounds used as Component (iv)) can comprise 0% to 4% (e.g., 0.2% to3.7% or 0.5% to 3.5%) by weight of the polyurethane insulation foamcomposition based on the total weight of the composition.

While the amount of catalyst depends on the reactivity requirements ofthe application, including geographic and seasonal requirements, theweight ratio of: (1) the tertiary amine catalyst of Formula (I) to (2)the amine catalyst containing at least one amine group and/or thenon-amine catalyst is at least 1:5 (e.g., at least 1:2, at least 1:1, atleast 2:1, or at least 5:1).

Component (v): Hydrophilic Carboxylic Acid Compound

The polyurethane insulation foam composition disclosed herein comprisesa one or more hydrophilic carboxylic acid compounds comprising thestructure of Formula (II).

(HO)_(n)—R′—(COOH)_(m)  Formula (II):

-   -   wherein        -   R′ is a divalent C₁-C₁₀ aliphatic hydrocarbon moiety, n and            m are both integers and wherein n 0 and m 1.

The divalent C₁-C₁₀ aliphatic hydrocarbon moiety can comprise alinear/branched aliphatic moiety comprising 1 to 10 carbon atoms.Suitable examples of such C₁-C₁₀ aliphatic hydrocarbon moieties includemethylene, ethylene, n-propylene, iso-propylene, n-butylene,isobutylene, n-amylene, n-decylene, 2-ethylhexylene, or combinationsthereof. While the aforementioned C₁-C₁₀ aliphatic hydrocarbon moietiesdo comprise two available substitution sites, it is contemplated thatadditional hydrogens on the hydrocarbon could be replaced with furthercarboxyl and/or hydroxyl groups.

Suitable compounds that can be used as Component (v) includemono-carboxylic (such as formic, acetic, propionic, butyric) acid,hydroxyl-carboxylic (such as glycolic, lactic, 2-hydroxy butaric) acid,di-carboxylic (such as malonic, glutaric maleic) acid, andhydroxyl-polycarboxylic (such as citric) acid, AGS acid, or combinationsthereof. AGS acid is a mixture of dicarboxylic acids (i.e., adipic acid,glutaric acid, and succinic acid) that is obtained as a by-product ofthe oxidation of cyclohexanol and/or cyclohexanone in the adipic acidmanufacturing process Suitable AGS acid that may be used as Component(v) include RHODIACID AGS (available from Solvay S.A.), DIBASIC ACID(available from Invista S.á.r.l), “FLEXATRAC-AGS-200 (available fromAscend Performance Materials LLC), and Glutaric acid, technical grade(AGS) (available from Lanxess A.G.).

As used herein, a carboxylic acid shall be deemed hydrophilic when 25 gmor more (e.g., 40 gm or more or 60 gm or more) of the carboxylic acid issoluble per 100 gm of water at 25° C.

Formic acid, acetic acid and lactic acid are the preferred hydrophiliccarboxylic acids. Formic acid and acetic acid are the most preferredhydrophilic carboxylic acids

Component (v) can comprise 0.1% to 4% (e.g., 0.15% to 3.5% or 0.2% to3%) by weight of the polyurethane insulation foam composition based onthe total weight of the composition.

Component (vi): Halogenated Olefin Compound

The polyurethane insulation foam composition disclosed herein comprisesa one or more halogenated olefin (“HFOs”) compounds that serves as ablowing agent for the polyurethane foam composition.

The halogenated olefin compound used as Component (vi) comprises atleast one haloalkene (e.g, fluoroalkene or chlorofluoroalkene)comprising from 3 to 4 carbon atoms and at least one carbon-carbondouble bond. Suitable compounds that may be used as Component (vi)include hydrohaloolefins such as trifluoropropenes, tetrafluoropropenes(e.g., tetrafluoropropene (1234)), pentafluoropropenes (e.g.,pentafluoropropene (1225)), chlorotrifloropropenes (e.g.,chlorotrifloropropene (1233)), chlorodifluoropropenes,chlorotrifluoropropenes, chlorotetrafluoropropenes, hexafluorobutenes(e.g., hexafluorobutene (1336)), or combinations thereof. In certainembodiments, the tetrafluoropropene, pentafluoropropene, and/orchlorotrifloropropene compounds used as Component (vi) has no more thanone fluorine or chlorine substituent connected to the terminal carbonatom of the unsaturated carbon chain (e.g., 1,3,3,3-tetrafluoropropene(1234ze); 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene(1225ye), 1,1,1-trifluoropropene, 1,2,3,3,3-pentafluoropropene,1,1,1,3,3-pentafluoropropene (1225zc), 1,1,2,3,3-pentafluoropropene(1225yc), (Z)-1,1,1,2,3-pentafluoropropene (1225yez),1-chloro-3,3,3-trifluoropropene (1233zd),1,1,1,4,4,4-hexafluorobut-2-ene (1336mzzm), or combinations thereof).

Other blowing agents that may be used in combination with the HFOsdescribed above include air, nitrogen, carbon dioxide,hydrofluorocarbons (“HFCs”), alkanes, alkenes, mono-carboxylic acidsalts, ketones, ethers, or combinations thereof. Suitable HFCs include1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane (HFC-134a),pentafluoroethane (HFC-125), 1,1,1,3,3-pentafluoropropane (HFC-245fa),1,1,1,3,3-pentaflurobutane (HFC-365mfc), or combinations thereof.Suitable alkanes and alkenes include n-butane, n-pentane, isopentane,cyclopentane, 1-pentene, or combinations thereof. Suitablemono-carboxylic acid salts include methyl formate, ethyl formate, methylacetate, or combinations thereof. Suitable ketones and ethers includeacetone, dimethyl ether, or combinations thereof.

Component (vi) can comprise 2% to 10% (e.g., 2.5% to 9% or 3% to 8%) byweight of the polyurethane insulation foam composition based on thetotal weight of the composition.

Component (vii): Stabilizing Compound

The polyurethane insulation foam composition disclosed herein comprisesone or more stabilizing compounds that assist in the overallstabilization of the polyurethane foam composition. For example,Component (vii) assists in the stabilization of a polyurethane foamcomposition that uses a compound having a electrophilic double bond(e.g., HFO-1233zd) as Component (v). Without Component (vii), there is apossibility of HFO-1233zd interacting with the tertiary amine compoundsused in Component (iv) which are nucleophilic by design. Theseunintended interactions can lead to the formation of unwanted compoundsin the composition thereby making it unstable. Component (vii) helpsshield or prevent such interactions with HFO-1233zd thereby enhancingthe overall stability of the polyurethane insulation foam composition.It is believed that, in some instances, Component (vii) forms aprotective hydration layer around Component (iv) which shields thecompound from HFO-1233zd.

Suitable compounds that can be used as Component (vii) includeun-alkoxylated polyhydroxy compounds having 4 or more hydroxyl groups.Examples of such compounds are sugar and sugar alcohols includingerythritol, arabitol, xylitol, sorbitol, mannitol, isomalt, lactitol,maltitol, xylose, glucose, fructose, sucrose, trehalose, lactose,raffinose, cyclodextrin, maltodextrin, corn syrup, amylopectin, orcombinations thereof.

In certain embodiments, Component (vii) is present in less than 10micro-moles (e.g., less than 5 micro-moles, less than 2 micro-moles) per100 gm of the polyurethane foam composition. In yet other embodiments, ahydrophilic carboxylic acid compound (i.e., Component (v)) is present inthe polyurethane insulation foam composition in an amount ranging from0.2 to 4 (e.g., 0.25 to 2, 0.3 to 1.5, or 0.3 to 1) equivalents ofcarboxyl group per equivalent of tertiary amines in the tertiary aminecompound (i.e., Component (iv)) while Component (vii) is present in anamount of less than 0.8 (e.g., less than 0.6, less than 0.5, or lessthan 0.4) moles per mole of Component (v).

Component (viii): Other Auxiliary Agents and Additives

The polyurethane insulation foam composition disclosed herein cancomprise various auxiliary agents and additives that are known in theart of isocyanate-based insulation foam technology. Suitable additivesinclude surfactant, fire retardants, smoke suppressants, cross-linkingagents, viscosity reducer, infra-red pacifiers, cell-size reducingcompounds, pigments, fillers, reinforcements, mold release agents,antioxidants, dyes, pigments, antistatic agents, biocide agents, orcombinations thereof.

Examples of suitable flame retardants that may be used in thepolyurethane insulation foam composition disclosed herein includeorgano-phosphorous compounds (e.g., organic phosphates, phosphites,phosphonates, polyphosphates, polyphosphites, polyphosphonates),ammonium polyphosphates (e.g., triethyl phosphate, diethy ethylphosphonate, and tris(2-chloropropyl)-phosphate); and halogenated fireretardants (e.g., tetrabromophthalate esters and chlorinated parrafins).

Examples of other suitable auxiliary agents and additives that may beused in the polyurethane insulation foam composition disclosed hereininclude triethanolamine and glycerol cross linking agents; propylenecarbonate and 1-methyl-2-pyrrolidinone viscosity reducers; carbon black,titanium dioxide, and metal flake infra-red opacifiers; inert, insolublefluorinated compounds, and perfluorinated cell-size reducing compounds;calcium carbonate fillers; glass fibers and/or ground up foam wastereinforcing agents; zinc stearate mold release agents; butylated hydroxytoluene antioxidants; azo-/diazo dyestuff and phthalocyanines pigments.

In certain embodiments, the surfactants used in the foam composition ofthe present disclosure can comprise one or more silicone or non-siliconebased surfactants. These surfactants are typically used to control thesize of the cells that form as the foam composition reacts to form thepolyurethane foam product thereby allowing for the control of theinternal cell structure of the foam product. In certain embodiments, afoam comprising a uniform set of small sized cells (e.g., <300 μm) isdesired because the foam will exhibit outstanding physical properties(e.g., compressive strength and thermal conductivity properties).Additionally, the aforementioned surfactants will also assist in thestabilization of the internal cells thereby ensuring that the cells donot collapse as the composition reacts to form the polyurethane foamproduct.

Suitable silicone surfactants that can be used in the polyurethaneinsulation foam composition disclosed herein include polyorganosiloxanepolyether copolymers and polysiloxane polyoxyalkylene block co-polymers(e.g., Momentive's L-5345, L-5440, L-6100, L-6642, L-6900, L-6942,L-6884, L-6972 and Evonik Industries AG's DC-193, DC5357, Si3102,Si3103, Tegostab B8490; B8496, B8536; B84205; B84210; B84501; B84701,B84715). Others silicone surfactants that can be used also are disclosedin U.S. Pat. No. 8,906,974 and U.S. Patent Publication No. US2016/0311961.

Non-silicone surfactants that can be used in the polyurethane insulationfoam composition disclosed herein include non-ionic, anionic, cationic,ampholytic, semi-polar, zwitterionic organic surfactants. Suitablenon-ionic surfactants include phenol alkoxylates and alkylphenolalkoxylates (e.g., ethoxylated phenol and ethoxylated nonylphenol,respectively). Other useful non-silicone non-ionic surfactants includeLK-443 (available from Evonik Industries AG) and VORASURF 504 (availablefrom Dow Chemicals).

Component (viii) can comprise 0.5% to 10% (e.g., 0.8% to 9% or 1% to 8%)by weight of the polyurethane insulation foam composition based thetotal weight of the composition.

In some embodiments, the polyurethane insulation foam composition doesnot contain a guanidine compound.

Processing

A polyurethane insulation foam product (e.g., a closed-cell polyurethaneinsulation foam product) may be made from the polyurethane insulationfoam composition disclosed herein via a one component, two component, ormulti-component (i.e., greater than two component) system. As usedherein, a polyurethane foam product shall be deemed to be a “closedcell” foam if the closed cell content of such foam is greater than 70%(e.g., 80% or 85%) as measured by ASTM D6226-15. Moreover, in certainembodiments, the polyurethane insulation foam product of the presentdisclosure would exhibit a thermal conductivity value (K-value) rangingfrom 0.10 to 0.16 Btu-in/hr·ft²° F. (e.g., 0.11 to 0.15 Btu-in/hr·ft²°F. or 0.12 to 0.1416 Btu-in/hr·ft²° F.) as measured by ASTM C518-17 ataverage plate temperature of 75° F. In a two component system, theB-Side of the polyurethane insulation foam composition, which istypically in a liquid state, is mixed with the A-Side of the compositionthereby activating polymerization of the reaction system. As will beunderstood by one skilled in the art, Component (i) of the polyurethaneinsulation foam composition disclosed herein will be in the A-Side of atwo component system while Component (ii) will be in the B-Side.However, it is noted that Components (iv), (v), (vi), (vii) and (viii)can be added to one or both of the A-Side and B-Side. In other words,Components (iv)-(viii) can be combined with one or both of Components(i) and (ii) simply based on the chemical and physical compatibility ofthe those compounds with Components (i) and (ii).

Regardless of the number of components used in connection with thepolyurethane insulation foam composition disclosed herein, the relativeproportions of the components may be metered, either by weight or byvolume, to provide a ratio of free isocyanate groups to the total of theisocyanate-reactive groups ranging from 0.9 to 5 (e.g., 0.95 to 4 or 1to 3.5) based on the total isocyanate and isocyanate reactive compoundspresent in the polyurethane insulation foam composition.

In certain embodiments, a polyurethane foam product may be made usingthe polyurethane insulation foam composition and a one-shot, prepolymeror semi-prepolymer technique together with a mixing method such asimpingement mixing. In other embodiments, after mixing, the polyurethaneinsulation foam composition (while still in a substantially liquidstate) may be dispensed into a cavity (i.e., cavity filling), molded,open poured (e.g., process for making slabstock), sprayed, frothed, orlaminated with facing materials such as paper, metal, plastics, orwood-board. Such foam products are useful in any insulating surfaces orenclosures such as houses, roofing, buildings, refrigerators, freezers,appliances, piping, and vehicles.

The preparation of polyurethane foams using the compositions describedherein may follow any of the methods well known in the art can beemployed (e.g., see Saunders and Frisch, Volumes I and II PolyurethanesChemistry and technology, 1962, John Wiley and Sons, New York, N.Y.; orOertel, Polyurethane Handbook 1985, Hanser Publisher, New York; orRandall and Lee, The Polyurethanes Book 2002).

Polyisocyanurate Foam Product

While the present disclosure has been focused on a polyurethaneinsulation foam composition and the resulting polyurethane foam product(e.g., a rigid, closed-cell polyurethane insulation foam product), thecomposition can also be used to form a polyisocyanurate foam product(e.g., a rigid, closed-cell polyisocyanurate foam product) simply byadding one or more trimerization catalysts to the reactive systemdisclosed herein. Suitable isocyanate trimerization catalysts that maybe added to Components (i)-(viii) include those listed above.Accordingly, in some embodiments, the polyurethane insulation foamcomposition is a polyisocyanurate insulation foam composition. It isnoted that the polyisocyanurate insulation foam composition would form apolyisocyanurate foam product that comprises both polyisocyanurate andpolyurethane reaction products.

In certain embodiments, the relative proportions of the components usedto form the polyisocyanurate insulation foam composition may be metered,either by weight or by volume, to provide a ratio of free isocyanategroups to the total of the isocyanate-reactive groups in a range of fromranging from 2 to 5 (e.g., 2.25 to 4) based on the total isocyanate andisocyanate reactive compounds present in the polyurethane insulationfoam composition.

Modifications

While specific embodiments of the disclosure have been described indetail, it will be appreciated by those skilled in the art that variousmodifications and alternatives to those details could be developed inlight of the overall teachings of the disclosure. Accordingly, theparticular arrangements disclosed are meant to be illustrative only andnot limiting as to the scope of the disclosure which is to be given thefull breadth of the claims appended and any and all equivalents thereof.Therefore, any of the features and/or elements which are listed abovemay be combined with one another in any combination and still be withinthe breadth of this disclosure.

EXAMPLES Components:

The following compounds are referred to in the examples:

Polyol 1: A polyether polyol having an OH value of 360 mg KOH/g made bypropoxylation of mixture of sucrose and diethylene glycol

Polyol 2: A polyether polyols made by propoxylation of mixture ofpolymethylene polyphenylene polyamine and diethylene glycol and blendedwith a viscosity reducer to give an OH value of 291 mg KOH/g

Polyol 3: A polyether polyol having an OH value of 650 mg KOH/g made bypropoxylation of glycerol

Polyol 4: A polyether polyol having an OH value of made by propoxylationof a mixture of polymethylene polyphenylene polyamine and diethyleneglycol.

Polyol 5: A polyether polyol having an OH value of 437 mg KOH/g made bypropoxylation of a mixture of polymethylene polyphenylene polyamine anddiethylene glycol and blended with a viscosity reducer to give an.

Sucrose: available from Research Products International

DABCO® 2040: A low odor amine catalyst used to enhance cure and adhesionin rigid polyurethane foam available from Evonik Industries AG.

JEFFCAT® ZF-20: Bis-(2-dimethylaminoethyl)ether catalyst available fromHuntsman Petrochemical LLC.

POLYCAT® 203: An amine based catalyst available from Evonik Nutrition &Care GmbH

JEFFCAT® DMCHA: N,N-dimethylcyclohexylamine catalyst available fromHuntsman Petrochemical LLC.

JEFFCAT® PMDETA: Pentamethyldiethylenetriamine catalyst available fromHuntsman Petrochemical LLC.

JEFFCAT® ZF-10: N,N,N′-trimethyl-N′-hydroxyethylbisaminoethylethercatalyst available from Huntsman Petrochemical LLC.

JEFFCAT® Z-110: N,N,N′-trimethylaminoethyl-ethanolamine catalystavailable from Huntsman Petrochemical LLC.

JEFFCAT® DMEA: N,N-dimethylethanolamine catalyst available from HuntsmanPetrochemical LLC.

JEFFCAT® ZR-70: 2-(2-dimethylaminoethoxy)ethanol catalyst available fromHuntsman Petrochemical.

Formic acid: Available from Aldrich Chemical.

D-Sorbitol: available from Research Products International.

TEGOSTAB® EP-A-69: A hydrolysis-resistant silicone surfactant availablefrom Evonik Industries AG.

TEGOSTAB© B8491: A hydrolysis-resistant silicone surfactant availablefrom Evonik Industries AG.

HFO-1233zd(E): 1-chloro-3,3,3-trifluoropropene available from HoneywellInternational Inc. as Solstice® LBA.

RUBINATE M: Polymeric MDI having an NCO value of 30.5% available fromHuntsman International LLC.

Description of the FOAM REACTIVITY TEST:

A composition's (e.g., the compositions described in Table 1) REACTIVESHIFT (i.e., CT REACTIVE SHIFT as calculated by FormulaX, TFT REACTIVESHIFT as calculated by Formula Y, and EOR REACTIVE SHIFT as calculatedby Formula Z) was calculated through the use various data pointsgathered via the FOAM REACTIVITY TEST. The FOAM REACTIVITY TESTcomprises the following steps: (i) equilibrating a composition's A-Side(polyol premix) and B-Side (isocyanate) to 15° C. by placing the A- andB-Side in a cooling thermostat (e.g., LAUDA Alpha RA 24 Coolingthermostat) (ii) pouring the contents of the equilibrated A-Side andB-Side into a 32-oz non-waxed paper cup (e.g., Solo H4325-2050) therebycombining the two components; (ii) mixing the combined components for 4seconds at 2500 rpm using a mechanical mixer (e.g., Caframo BDC3030stirrer); (iii) allowing the components of the composition to reactthereby forming the polyurethane foam product; and (iv) measuring one ormore of the composition's CT, TFT, and/or EOR (each defined below)during the formation of the polyurethane foam product.

For purposes of this disclosure, the following terms shall be defined asfollows:

Cream Time (“CT”) means the elapsed time between the moment acomposition's isocyanate component is mixed with the composition'sisocyanate reactive component and the formation of the fine froth orcream in the composition.

Tack Free Time (“TFT”) means the elapsed time between the moment acomposition's isocyanate component is mixed with the composition'sisocyanate reactive component and the point at which the outer skin ofthe foam loses its stickiness or adhesive quality. Experimentally, suchloss of stickiness is when a 6″ wooden tongue depressor (e.g., Puritan705) is brought into contact with the surface of the reaction mixtureand appears non-sticky when it is removed from the surface.

End of Rise Time (“EOR”) means the elapsed time between the moment acomposition's isocyanate component is mixed with the composition'sisocyanate reactive component and the point at which the foam rise iscomplete.

Calculation of REACTIVE SHIFT:

A composition's CT REACTIVE SHIFT was calculated using Formula X:

CT REACTIVE SHIFT=100*[(CT₇₉−CT₀)/CT₀]  Formula X:

-   -   wherein        -   CT₇₉ means a composition's CT as determined using the FOAM            REACTIVITY TEST after the composition's B-Side has been aged            at 40° C. in a closed, pressure-rated, glass container            (e.g., ACE GLASS Pressure Bottle (#8648-251)) that was            placed in an oven (e.g., VWR 1370GM oven) for 79 days.        -   CT₀ means a composition's CT as determined using the FOAM            REACTIVITY TEST after the composition's B-Side has been aged            at 40° C. in a closed, pressure-rated, glass container            (e.g., ACE GLASS Pressure Bottle (#8648-251)) that was            placed in an oven (e.g., VWR 1370GM oven) for 0 days.

A composition's TFT REACTIVE SHIFT was calculated using Formula Y:

TFT REACTIVE SHIFT=100*[(TFT₇₉−TFT₀)/TFT₀]  Formula Y:

-   -   wherein        -   TFT₇₉ means a composition's TFT as determined using the FOAM            REACTIVITY TEST after the composition's B-Side has been aged            at 40° C. in a closed, pressure-rated, glass container            (e.g., ACE GLASS Pressure Bottle (#8648-251)) that was            placed in an oven (e.g., VWR 1370GM oven) for 79 days.        -   TFT₀ means a composition's TFT as determined using the FOAM            REACTIVITY TEST after the composition's B-Side has been aged            at 40° C. in a closed, pressure-rated, glass container            (e.g., ACE GLASS Pressure Bottle (#8648-251)) that was            placed in an oven (e.g., VWR 1370GM oven) for 0 days.

A composition's EOR REACTIVE SHIFT was calculated using Formula Z:

EOR REACTIVE SHIFT=100*[(EOR₇₉−EOR₀)/EOR₀]  Formula Z:

-   -   wherein        -   EOR₇₉ means a composition's EOR as determined using the FOAM            REACTIVITY TEST after the composition's B-Side has been aged            at 40° C. in a closed, pressure-rated, glass container            (e.g., ACE GLASS Pressure Bottle (#8648-251)) that was            placed in an oven (e.g., VWR 1370GM oven) for 79 days.        -   EOR₀ means a composition's EOR as determined using the FOAM            REACTIVITY TEST after the composition's B-Side has been aged            at 40° C. in a closed, pressure-rated, glass container            (e.g., ACE GLASS Pressure Bottle (#8648-251)) that was            placed in an oven (e.g., VWR 1370GM oven) for 0 days.

It should be noted that in some embodiments, the temperature used to agea composition's B-side as described above can range from 30° C. to 40°C. (e.g, 30° C. to 55° C.).

Table 1:

Table 1 shows various data points for four polyurethane compositionsused to make a polyurethane foam product. The B-side for eachcomposition was aged at 40° C. in a in an ACE GLASS Pressure Bottle(#8648-251) and placed in a VWR 1370GM oven for the total number of dayslisted in Table 1. When a particular day was reached (e.g., at Day 22,57 or 79), the B-side was taken out of the oven and placed in a waterbath at 15° C. Once the polyol premix reached bath temperature, visualinspection of the polyol premix was made to assess whether it was clearor cloudy and whether a precipitate (abbreviated as “ppt” in the Tablesdisclosed herein) can be seen at the bottom of container. After thevisual inspection, a foam product was made using the steps of the FOAMREACTIVITY TEST (described above) and the composition's REACTIVE SHIFT(i.e., CT REACTIVE SHIFT as calculated by Formula X, TFT REACTIVE SHIFTas calculated by Formula Y, and EOR REACTIVE SHIFT as calculated byFormula Z) was calculated using data points measured during the FOAMREACTIVE TEST.

It should be noted that a foam product was made for each day that isrepresented in the Tables (e.g., Day 0, 22, 57, or 79).

TABLE 1 Formulations Foams A B Polyol Premix Polyol 1 49.5 49.5 Polyol 211.6 11.6 Polyol 3 20.7 20.7 TEGOSTAB ® EP-A-69 2.0 2.0 DABCO ® 2040 1.51.5 JEFFCAT ® ZF-20 0.1 0.1 Formic acid 0.9 0.9 Water 1.9 1.9 Sucrose0.5 D-Sorbitol 0.5 HFO-1233zd[E] 11.3 11.3 Total Polyol Premix 100.0100.0 Isocyanate Rubinate M 148.5 148.5 Isocyanate/Premix ratio 1.491.49 Aging time at 40° C., (days) 0 0 Foam CT/GT/TFT (sec)* 10/81/12310/83/126 Free Rise Density, pcf 1.88 1.81 Aging time at 40° C., (days)22 22 Foam CT/GT/TFT (sec)* 10/80/127 10/82/127 Free Rise Density, pcf1.88 1.78 Aging time at 40° C., (days) 57 57 Foam CT/GT/TFT (sec)*11/81/124 11/82/125 Free Rise Density, pcf 1.87 1.81 Aging time at 40°C., (days) 79 79 Foam CT/GT/TFT (sec)* 12/82/128 12/84/129 Free RiseDensity, pcf 1.85 1.78 CT REACTIVITY SHIFT** 20 20 GT REACTIVITY SHIFT**1 1 TFT REACTIVITY SHIFT** 4 2 *CT, GT & TFT are defined above**Calculated as described above

It should also be noted that the foam products made from thecompositions for Foams A and B (all of which represent certainembodiments of the present disclosure) had internal excellent appearance(e.g., uniform internal cell size and free of internal voids) and hadfine internal cells with no evidence of cell collapse. In other words,good quality foam product was produced using the compositions disclosedherein irrespective of whether the polyol premix used was fresh or aged.

Table 2:

Table 2 shows various data points for three polyurethane compositionsused to make a polyurethane foam product. The preparation proceduresused in connection with the polyurethane compositions listed in Table 1were followed for these polyurethane compositions except the exact dayswhen the B-side was taken out of the oven and placed in a water bath wasat Day 11, 14, 49, or 79. It is noted that these polyurethanecompositions did not use one or more embodiments of the presentdisclosure. More specifically, Formulation “C” did not use Component(vii) (i.e., a stabilizing compound); Formulation “E” did not useComponent (v) (i.e., a hydrophillic carboxylic acid compound); andFormulation “D” did not use either Component (vii) or Component (v).

TABLE 2 Formulations Foams C D E Polyol Premix Polyol 1 49.4 49.6  49.4 Polyol 2 11.6 Polyol 3 20.7 20.8  20.7  Polyol 4 6.8 6.8 TEGOSTAB ®EP-A-69 2.0 TEGOSTAB ® B8491 1.6 1.6 DABCO ® 2040 1.6 POLYCAT ® 203 0.90.9 JEFFCAT ® ZF-20 0.1 0.4 0.4 Formic acid 0.9 Water 2.3 1.7 1.7Sucrose 0.0 0.5 HFO-1233zd[E] 11.3 18.2  18.1  Total Polyol Premix 100.0100.0  100.0  Isocyanate Rubinate M 148.40 141.00  141.00 Isocyanate/Premix ratio 1.48  1.41  1.41 Aging time at 40° C., (days) 00   0   Foam CT/GT/TFT (sec)* 10/78/130 10/96/129 10/98/134 Free RiseDensity, pcf 1.85  1.83  1.77 Aging time at 40° C., (days) 14 11   11  Foam CT/GT/TFT (sec)* 11/83/135 14/144/237 13/124/178 Free Rise Density,pcf 1.83  1.86  1.79 Aging time at 40° C., (days) 49 Foam CT/GT/TFT(sec)* 11/86/132 Free Rise Density, pcf 1.80 Aging time at 40° C.,(days) 79 Foam CT/GT/TFT (sec)* 13/88/136 Free Rise Density, pcf 1.84 CTREACTIVITY SHIFT** 30 >>40    >>30    GT REACTIVITY SHIFT**13 >>50    >>27    TFT REACTIVITY SHIFT** 5 >>84    >>33    *CT, GT &TFT are defined above **Calculated as described above

When fresh (i.e. Day 0 or non-aged) polyol premix was used, thepolyurethane foam products made from Formulations C, D and E had auniform small cell structure with no voids. There was a loss inreactivity of Foam C as the aging time increased (see CT, GT and TFTreactivity shift of 30, 13, 5, respectively after 79 days of pre-blendaging at 40° C.).

For Formulations D and E the loss in reactivity was very large justafter 11 days of pre-blend aging time. After just 11 days of pre-blendaging, the foam products made from Formulations D and E had a very poorappearance (e.g, course internal cells, many internal voids and evidenceof cell collapse). In other words, a poor quality foam product wasproduced from Formulations D and E even though the pre-blend aging timewas just 11 days. Due to these results, the aging of Formulations D andE was discontinued after 11 days, but it is reasonable to assume that aloss in reactivity would have continued (see CT, GT and TFT reactivityshift was significantly higher than 40, 50, 84, respectively, for Foam Dand 30, 27, 33 respectively, for Foam E).

Table 2 shows that the foam compositions that did not use one or moreembodiments of the present disclosure exhibited a significant loss inreactivity and in some cases foam collapse when pre-blend was aged.

Table 3:

Table 3 shows various data points for five polyurethane compositionsused to make a polyurethane foam product per teachings of the presentdisclosure.

TABLE 3 Formulations Foams F G H I J Polyol Premix Polyol 1 51.3 51.351.2 51.0 51.3 Polyol 5 8.0 8.0 8.0 8.0 8.0 Polyol 3 21.5 21.5 21.4 21.321.4 TEGOSTAB ® EP-A-69 2.1 2.1 2.1 2.1 2.1 DABCO ® 2040 1.8 1.8 1.8 1.81.8 JEFFCAT ® PMDETA 0.2 JEFFCAT ® ZF-10 0.2 JEFFCAT ® Z-110 0.5JEFFCAT ® DMEA 0.9 JEFFCAT ® ZR-70 0.3 Formic acid 1.0 1.0 1.0 1.0 1.0Water 1.8 1.8 1.8 1.8 1.8 Sucrose D-Sorbitol 0.5 0.5 0.5 0.5 0.5HFO-1233zd[E] 11.8 11.8 11.7 11.7 11.7 Total Polyol Premix 100.0 100.0100.1 100.0 100.0 Isocyanate Rubinate M 154.7 154.7 154.4 153.6 154.5Isocyanate/Premix ratio 1.55 1.55 1.54 1.54 1.55 Aging time at 40° C.,(days) 0 0 0 0 0 Foam CT/GT/TFT (sec)* 11/81/114 11/82/116 11/83/11711/84/122 11/85/122 Free Rise Density, pcf 2.00 2.01 1.99 2.00 2.00Aging time at 40° C., (days) 29 29 29 29 29 Foam CT/GT/TFT (sec)*11/81/114 11/86/124 11/85/116 11/87/124 11/87/124 Free Rise Density, pcf1.92 2.02 1.97 2.00 2.00 Aging time at 40° C., (days) 48 48 48 48 48Foam CT/GT/TFT (sec)* 10/83/120 11/86/124 10/85/122 11/86/127 10/84/124Free Rise Density, pcf 1.98 2.03 1.98 1.98 2.00 Aging time at 40° C.,(days) 79 79 79 79 79 Foam CT/GT/TFT (sec)* 11/81/116 12/85/12212/85/122 11/85/125 12/87/125 Free Rise Density, pcf 2.02 2.02 2.06 1.982.02 CT REACTIVITY SHIFT** 0 9 9 0 9 GT REACTIVITY SHIFT** 0 4 2 1 2 TFTREACTIVITY SHIFT** 2 5 4 2 2 *CT, GT & TFT are defined above**Calculated as described above

Reactivity shifts for Formulations F, G, H, I and J were low and goodquality foam products were made irrespective of the age of the polyolpremix used. The foams had excellent internal appearance (e.g., uniforminternal cell size and free of internal voids) with uniform cell sizeand free of voids.

Table 4:

Table 4 shows various data points for two additional polyurethanecompositions used to make a polyurethane foam product according toembodiments of the present disclosure

TABLE 4 Formulations Foams K L Polyol Premix Polyol 1 49.1 48.8 Polyol 211.5 11.5 Polyol 3 20.5 20.4 TEGOSTAB ® EP-A-69 2.0 2.0 DABCO ® 2040 0.30.0 JEFFCAT ® DMCHA 1.9 2.9 JEFFCAT ® ZF-20 0.1 0.1 Formic acid 0.9 1.2D-Sorbitol 0.5 0.5 Water 1.7 1.4 HFO-1233zd[E] 11.3 11.2 Total PolyolPremix 100.0 100.0 Isocyanate Rubinate M 148.1 147.2 Isocyanate/Premixratio 1.48 1.47 Aging time at 40° C., (days) 0 0 Foam CT/GT/TFT (sec)*14/85/126 14/79/113 Free Rise Density, pcf 1.88 1.91 Aging time at 40°C., (days) 29 29 Foam CT/GT/TFT (sec)* 13/84/122 12/78/114 Free RiseDensity, pcf 1.85 1.89 Aging time at 40° C., (days) 43 43 Foam CT/GT/TFT(sec)* 14/85/121 14/79/114 Free Rise Density, pcf 1.88 1.94 Aging timeat 40° C., (days) 79 79 Foam CT/GT/TFT (sec)* 14/82/122 14/76/112 FreeRise Density, pcf 1.91 1.94 CT REACTIVITY SHIFT** 0 0 GT REACTIVITYSHIFT** −4 −4 TFT REACTIVITY SHIFT** −3 −1 *CT, GT & TFT are definedabove **Calculated as described above

Formulations Foams K and I made good quality foam irrespective ofwhether the polyol premix used was fresh or aged. The foam had goodinternal appearance with uniform cell size and free of voids.

1. A polyurethane insulation foam composition comprising: (i) anaromatic isocyanate compound; (ii) an isocyanate reactive compound;(iii) water; (iv) a tertiary amine compound (v) a hydrophilic carboxylicacid compound (vi) a halogenated olefin blowing agent; and (vii) astabilizing compound wherein the stabilizing compound comprises anun-alkoxylated polyhydroxy compound having 4 or more hydroxyl groups;(viii) optionally, other additives; and wherein Component (v) is presentin the polyurethane insulation foam composition in an amount rangingfrom 0.2 to 4 equivalents of carboxyl group per equivalent of tertiaryamines in Component (iv) and Component (vii) is present in an amount ofless than 0.8 moles per mole of Component (v).
 2. The polyurethaneinsulation foam composition according to claim 1, wherein thepolyisocyanate comprises diphenylmethane diisocyanate, polyphenylenepolymethylene polyisocyanate, tolylene diisocyanate,1,5-naphtalenediisocyanate, p-phenylenediisocyanate, tolidinediisocyanate, or combinations thereof.
 3. The polyurethane insulationfoam composition according to claim 1, wherein Component (ii) comprisesa polyether polyol, polyester polyol, hydroxyl-terminatedpolythioethers, polyamides, polyesteramides, polycarbonates,polyacetals, polyolefins, polyamines, polythiols, polysiloxanes,glycols, or combinations thereof.
 4. The polyurethane insulation foamcomposition according to claim 1, wherein Component (iv) furthercomprises of bis-(2-dimethylaminoethyl)ether;N,N,N′-trimethyl-N′-hydroxyethylbisaminoethylether;N,N-dimethylethanolamine; N,N-dimethylcyclohexylamine;N-methyldicyclohexylamine; benzyldimethylamine;pentamethyldiethylenetriamine;N,N,N′,N″,N″-pentamethyldipropylenetriamine;N′-(3-(dimethylamino)propyl-N,N-dimethyl-1,3-propanediamine;2-(2-dimethylaminoethoxy)ethanol;N,N,N′-trimethylaminoethyl-ethanolamine;2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol;N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether;N,N,N′,N′-tetramethylenediamine; N-ethylmorpholine;2,2′dimorpholinodiethylether;1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine;1,2-dimethlyimidazol; N-methyl-,N′-(2-dimethylamino)ethyl-piperazine;N,N-dimethylaminoethyl morpholine and triethylene diamine combinationsthereof.
 5. The polyurethane insulation foam composition according toclaim 1, wherein Component (v) comprises the structures of followingformula:(HO)_(n)—R′—(COOH)_(m) wherein R′ is a divalent C₁-C₁₀ aliphatichydrocarbon moiety, n and m are both integers and wherein n 0 and m 1,or combinations thereof.
 6. The polyurethane insulation foam compositionaccording to claim 1, wherein Component (v) comprises of formic acid,acetic acid, lactic acid or combinations thereof.
 7. The polyurethaneinsulation foam composition according to claim 1, wherein Component (vi)comprises trifluoropropenes, tetrafluoropropenes, pentafluoropropenes,chlorotrifloropropenes, chlorodifluoropropenes, chlorotrifluoropropenes,chlorotetrafluoropropenes, hexafluorobutenes, or combinations thereof.8. The polyurethane insulation foam composition according to claim 1,wherein Component (vi) comprises trans-1-chloro-3,3,3-trifluoropropene;(z)-1,1,1,4,4,4-hexafluorobut-2-ene; trans-1,3,3,3-tetrafluoroprop-1-eneor combinations thereof.
 9. The polyurethane insulation foam compositionaccording to claim 1, wherein Component (vii) comprises erythritol,arabitol, xylitol, sorbitol, mannitol, isomalt, lactitol, maltitol,xylose, glucose, fructose, sucrose, trehalose, lactose, raffinose,cyclodextrin, maltodextrin, corn syrup, amylopectin, or combinationsthereof.
 10. The polyurethane insulation foam composition according toclaim 1, wherein Component (viii) comprise a secondary blowing agentcomprising air, nitrogen, carbon disoxide, hydrofluoroalkanes, alkanes,alkenes, mono-carboxylic acid salts, ketones, ethers, or combinationsthereof.
 11. A method of making a polyurethane foam product from apolyurethane insulation foam composition comprising: reacting one ormore of the following reactive ingredients of the polyurethaneinsulation foam composition to form the polyurethane foam product: (i)an aromatic isocyanate compound; (ii) an isocyanate reactive compound;(iii) water; (iv) a tertiary amine compound; (v) a hydrophiliccarboxylic acid; (vi) a halogenated olefin blowing agent; and (vii) astabilizing compound wherein the stabilizing compound comprises anun-alkoxylated polyhydroxy compound having 4 or more hydroxyl groups;(viii) optionally, other additives; wherein Component (v) is present inthe polyurethane insulation foam composition in an amount ranging from0.2 to 4 equivalents of carboxyl group per equivalent of tertiary aminesin Component (iv) and Component (vii) is present in an amount of lessthan 0.8 moles per mole of Component (v); wherein the CT REACTIVITYSHIFT of the polyurethane insulation foam composition is less than orequal to 20 and the TFT REACTIVITY SHIFT is less than or equal to 4; andwherein the CT REACTIVITY SHIFT and the TFT REACTIVITY SHIFT of thepolyurethane insulation foam composition is determined by using FormulasX and Y, respectively:CT REACTIVE SHIFT=100*[(CT₇₉−CT₀)/CT₀]  Formula X: wherein CT₁₇ means acomposition's CT as determined using the FOAM REACTIVITY TEST after thecomposition's B-Side comprising Components (ii) and (iii) has been agedat 40° C. in a closed, pressure-rated, glass container that was placedin an oven for 79 days. CT₀ means a composition's CT as determined usingthe FOAM REACTIVITY TEST after the composition's B-Side comprisingComponents (ii) and (iii) has been aged at 40° C. for 0 days. andTFT REACTIVE SHIFT=100*[(TFT₇₉−TFT₀)/TFT₀]  Formula Y: wherein TFT₁₇means a composition's TFT as determined using the FOAM REACTIVITY TESTafter the composition's B-Side comprising Components (ii) and (iii) hasbeen aged at 40° C. in a closed, pressure-rated, glass container thatwas placed in an oven for 79 days. TFT₀ means a composition's TFT asdetermined using the FOAM REACTIVITY TEST after the composition's B-Sidecomprising Components (ii) and (iii) has been aged at 40° C. for 0 days.12. The method according to claim 12, wherein the polyisocyanatecomprises wherein the polyisocyanate comprises diphenylmethanediisocyanate, polyphenylene polymethylene polyisocyanate, tolylenediisocyanate, 1,5-naphtalenediisocyanate, p-phenylenediisocyanate,tolidine diisocyanate, or combinations thereof.
 13. The method accordingto claim 11, wherein Component (ii) comprises a polyether polyol,polyester polyol, hydroxyl-terminated polythioethers, polyamides,polyesteramides, polycarbonates, polyacetals, polyolefins, polyamines,polythiols, polysiloxanes, glycols, or combinations thereof.
 14. Themethod according to claim 11, wherein Component (iv) further compriseswherein Component (iv) further comprises ofbis-(2-dimethylaminoethyl)ether;N,N,N′-trimethyl-N′-hydroxyethylbisaminoethylether;N,N-dimethylethanolamine; N,N-dimethylcyclohexylamine;N-methyldicyclohexylamine; benzyldimethylamine;pentamethyldiethylenetriamine;N,N,N′,N″,N″-pentamethyldipropylenetriamine;N′-(3-(dimethylamino)propyl-N,N-dimethyl-1,3-propanediamine;2-(2-dimethylaminoethoxy)ethanol;N,N,N′-trimethylaminoethyl-ethanolamine;2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol;N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether;N,N,N′,N′-tetramethylenediamine; N-ethylmorpholine;2,2′dimorpholinodiethylether;1,3,5-tris(3-(dimethylamino)propyl)-hexahydro-s-triazine;1,2-dimethlyimidazol; N-methyl-,N′-(2-dimethylamino)ethyl-piperazine;N,N-dimethylaminoethyl morpholine and triethylene diamine combinationsthereof.
 15. The method according to claim 11, wherein Component (v)comprises a Waste AGS Acid Compound, a Natural Acid Compound, orcombinations thereof.
 16. The method according to claim 11, whereinComponent (vi) comprises trifluoropropenes, tetrafluoropropenes,pentafluoropropenes, chlorotrifloropropenes, chlorodifluoropropenes,chlorotrifluoropropenes, chlorotetrafluoropropenes, hexafluorobutenes,or combinations thereof.
 17. The method according to claim 11, whereinComponent (vi) comprises trans-1-chloro-3,3,3-trifluoropropene;(z)-1,1,1,4,4,4-hexafluorobut-2-ene; trans-1,3,3,3-tetrafluoroprop-1-eneor combinations thereof
 18. The polyurethane insulation foam compositionaccording to claim 11, wherein Component (vii) comprises erythritol,arabitol, xylitol, sorbitol, mannitol, isomalt, lactitol, maltitol,xylose, glucose, fructose, sucrose, trehalose, lactose, raffinose,cyclodextrin, maltodextrin, corn syrup, amylopectin, or combinationsthereof.
 19. The method according to claim 11, wherein Component (viii)comprise a secondary blowing agent comprising air, nitrogen, carbondisoxide, hydrofluoroalkanes, alkanes, alkenes, mono-carboxylic acidsalts, ketones, ethers, or combinations thereof.
 20. A polyurethane foamcomposition comprising: (i) an aromatic isocyanate compound; (ii) anisocyanate reactive compound; (iii) water; (iv) a tertiary aminecompound; (v) a hydrophilic carboxylic acid; (vi) a halogenated olefinblowing agent; and (vii) a stabilizing compound wherein the stabilizingcompound comprises an un-alkoxylated polyhydroxy compound having 4 ormore hydroxyl groups; (viii) optionally, other additives; whereinComponent (vii) is present in the polyurethane insulation foamcomposition in an amount less than 10 micro-moles per 100 gm of thepolyurethane foam composition.
 21. The polyurethane foam compositionaccording to claim 21, wherein the rigid polyurethane foam compositionis a spray foam composition for use in a spray application orpour-in-place composition for use in a pour-in-place application. 22.The polyurethane insulation foam composition according to claim 21,wherein Component (vii) comprises erythritol, arabitol, xylitol,sorbitol, mannitol, isomalt, lactitol, maltitol, xylose, glucose,fructose, sucrose, trehalose, lactose, raffinose, cyclodextrin,maltodextrin, corn syrup, amylopectin, or combinations thereof.